Vat dyes



Patented Apr. 6, 1937 UNITED STATES PATENT OFFICE VAT DYES Walter Hagge and Karl Haagen, Dessau in Anhalt, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application January 3, 1936, Serial No. 57,365. In Germany January 12, 1935 7 Claims. (Cl. 260-17) Our present invention relates to a process for the mass. After subsequently stirring for about manufacturing vat dyes and tothe new products an hour at the same temperature and then coolobtainable by this process. ing the mass is poured on to ice, the solid mat- By the present invention there are obtained ter filtered and washed. The product thus obfrom decacyclene valuable vat dyes by treating tained dissolves onlyin traces when boiled with 5 decacyclene successively or simultaneously with sodium sulfide. It can be vatted with caustic a sulfurizing agent and a halogenating agent in soda lye and hydrosulfite and the vat dyes cotton the presence of chloro-sulfonic acid; for ex? clear orange tints similar to those referred to in ample, by the action of sulfur, sulfur-chloride, Example 1. The yield of vat dye amounts to 59 10 or the like on decacyclene at a high temperature parts. 10 there is obtained a fused mass which by further Example 3.--Into 400 parts of chlorosulfonic treatment with a halogen at a lower temperature acid there are introduced, whilst cooling to about in presence of chlorosulfonic acid becomes a vat 20 C. and stirring, 50 parts of decacyclene and dye that dyes cotton in a hydrosulfite vat orange then 45 parts of sulfur. The temperature is tints. The dyes are characterized by good propraised in the course of 3 hours to 50 C. and main- 15 erties of fastness. tained at this point for about another 3 hours The dyes of equally good properties and similar during which time about 60 parts of chlorine are tint are obtained by the action of sulfur and gradually introduced whilst stirring. When cool halogen on decacyclene in chlorosulfonic acid in the mass is poured upon ice and the solid matter a single operation. Instead of halogen and sulfiltered and washed. This product is not soluble 20 fur there may be used agents, which, like sulfur in sodium sulfide but it dissolves in a hydrosulchloride, act simultaneously to produce halogenafite vat and the latter then dyes cotton a fast tion and sulfurization. orange tint. The yield of vat dye amounts to 110 The following examples illustrate the invenparts. tion, the parts being by weight: Similar vat dyes are obtainable by halogena- 25 Example 1.-Into 350 parts of chlorosulfonic tion of sulfur dyes made from hydroxydecacyacid are introduced, whilst stirring and cooling clene or decacyclene sulfonic acids. to about 15 to 20 C., 45 parts of decacyclene and In our copending application Serial No. 57,364 then 85 parts of sulfur chloride. In the course we have disclosed a process for manufacturing 0 of about 3 hours the temperature is raised to 50 sulfur dyes by heating decacyclene with a sul- C. and maintained at that point for 4 to 5 hours. furizing agent. In contradistinction thereto, our After cooling to room temperature the mass is present invention relates to a process for manupoured on to ice, the product filtered and the facturing vat dyes which are insoluble in alkali solid matter washed with water. By boiling for 2 metal sulfides but may be vatted with the aid of hours with 3 times its weight of crystallized hydrosulfite. These differentiated products. are 35 sodium sulfide under reflux and stirring with obtained by not only sulfurizing decacyclene, but water a part of the product is dissolved; the soby a further chlorination and treatment in the lution dyes cotton copper-brown tints of good presence of chlorosulfonic acid. fastness. The proportion which is insoluble in What we claim is:-

40 sodium sulfide may be vatted easily with hydro- 1. The process which comprises sulfurizing and 40 sulfite and the vat dyes cotton full orange tints halogenizing decacyclene in the presence of of good fastness. The yield of vat dyesaamounts chlorosulfonic acid.

to 60 parts. 2. The process which comprises simultaneously Example 2.-100 parts of decacyclene and 400 sulfurizing and halogenizing decacyclene in the parts of sulfur chloride are heated together in an presence of chlorosulfonicacid. 45 oil bath under reflux and whilst stirring to 200 3. The process which comprises sulfurizing C. (oil bath temperature). The mixture, which at and halogenizing decacyclene successively in the first is a dark red solution becomes highly viscous presence of chlorosulfonic acid. and then is further baked at 2'70 to 280 C. for -4. The process which comprises sulfurizing and about 8 hours for completing the formation of the chlorinating decacyclene with sulfur chloride at 50 a temperature between about 15 to about 50 50 parts of this crude dye are suspended in 300 C. in the presence of chlorosulfonic acid. parts of chlorosulfonic acid while gradually 5. The process which comprises sulfurizing raising the temperature to 90 C. in the course of decacyclene at a temperature up to about 280 about 5 hours. '75 parts of chlorine is passed into C., after cooling suspending the sulfur dye formed 55 in ohlorosulfonic acid, warming the mixture up to about 90 C. and passing chlorine into the mass.

6. The process which comprises introducing 5 decacyclene and sulfur into chlorosulfonio acid, warming the mixture to 50 C. and introducing chlorine into the mass.

7. Vat-dyes being difficultly soluble in a sodium sulfide solution but being easily vatted with hydrosulfite and dyeing cotton from this vat full orange tints of good fastness, these dyes being obtainable according to the process claimed in claim 1.

WALTER HAGGE. KARL HAAGEN. 

